Carbazole-indophenol compounds and process of preparing the same



do not condense readily with nitro rnrrz BALLAUF, FRIEDRICH mo'rar ann ALpnitq -soHM-E ima o1? nLnnannnn; an;

COBIQRATION OF DELAWARE Y cmAzoLm unornENo comrou Io Drawing. Original application filed January 16,

ans ANDyIiRbQESSaQE'i ARIiiGiagaiasm 1925, Serial mam, at in Gaaaaa aa,;a;

Y 1924. Pivided and this application filed Noyeniber; 6,; 1926, Serial lio lflfigfi b Y We have inyented new and usefulirnprovements in the manufacture of dyestuif intermediates ofwhich the following is a specification. This isa division of Ser. No. 2,926, filed on January 16, 1925, which has matured a into Patent No. 1,67 5,47 8 dated July3, 192 8.- 7 Our present invention consists in the pro duction of the new carbazoloic-acidarylidindophenols which wehave found to be valuacids themselves, i. e. Y OOOH 1 NH r V Carbazole-l-carboxylic acid 1 NH 0001?! Carba zo1e2-carboxy1ic acid V 1 i NH Carbazole-S-carboxylic acid v r i V Y i Y :COOH

so-phenols to the corresponding. indophenols, we have found that by reacting with primary and see I ondary aliphatic amines in presence of con-;

- densing agents upon carbazoloic acids, car- 5:1} bazoloic-acid-all;ylamides of the following type are obtained :Y

radical) and these condense easily yvith nitrosophenols The bazole 1 and the 'carbazole-2-carboxylic acids being the most easilytechnicallyac- 1Q able intermediates for the production of sulphide vat dyestuffs. .-Whereas the'carbazoloic' h il i e e a r (in which formula stands for hydrogen or an alkyl radical and Y for an alkyljx different carbazole- 11 carboxylic acids can be used, though the car,-

i 'Ea mple;-l2nertsbywe el ofmibflel? 2-carboxylic aeidfare dissol'yedgto -100Qpa ts q en andatt ilin t mp a u elei toluene,din ethylamineis"bubbledfthrough a ll? blli ib l h fi m l m i p s,il ld f ridi l'- d on?O p P ms,t i hl de,fi iit li id mo free a iba i e acid-{ nz eet d' n melt becomes oleafr andftransparent; Thej2; I I fcarbazolic acid -dimethyl amide isfinsolue av impste r an so rents s. W

was

W te fe ns ic lkj solutipns a wi e, bu -eas y ub e n, mere sulfuric; acids (from nitr n siin ol 1. paring y; luble-I 1 and.dissolveddn2150partsbyeight: o-iiicon eight of nitrosoplienolare ldissolveddn a169, aparts.jofconcentrated,"sulfuric acid of about pouredaonice, thereddish-blue coloredindo hQQ-QL i's'ffiltei'ed,.ofizz.-ia Y 1 Pee-e21 and'th. ar aie er ibX l e@idi tsdes rib byBOr Qhe (B t-49" 381.)! an i-J- is n t limit d he us vefi 'hi aminq ily Y [t n-i T e e vent snowd stil ed 0 or he esid ed e te withWate n he W ter;

a ch80 Theaniide as -obtainediintheabove is zdriedl i eentratedisnlfuric acid1669;G.; 27.5;partsab y: V e 1 gaefggboth solutions arejkcool ed mixed. Q i Aftera shorty while -thereaction iinassI 'is It has the formula:

The indophenol dissoli es in alcohol with a reddish-blue color and in concentrated sul furlc acid with a greenish-blue color.v In" alkaline solution; the indopheno'l is readily reduced by sodium-sulfide, or hydrosulfide (NaSH) to the corresponding leuco-indophenoh- Thelatter can alsobe obtained directly by ponringthe reaction mass in sul- 'furic acid upon a solution of caustic soda diluted with a large amount of ice, reducing.

this solution and precipitating theleuco-inlinked tothenitro e'n in resence of an ani a b P. ,7 hydroush'ahde condensation'agent, upon a i uric acid.

carbazole-c arboxylic acid and "condensing the so obtainedca a tnitrosophenol. r

' 2. In the process of preparing carbazoloicacid alkylamidojindophenols rbazoloic acidalkylamide with the Qsteps y whichicomprise reacting-with anjalipliatic" v c aminehaving a replaceable'hydrogen atom, linkedit'o the nitrogen, in presence of phoswhich is a reddish-blue powder soluble in concentrated sulfuric acid with a reddishs: blue color being readily'reduced to the corresponding leuco-compound when treated in alkaline solution with sodium sulfide or hy- In testimony wher eofwe have hereuntojset our hands. i p p i fL'FRITZfBALLAUF;

"FRIEDRICH MUTH;

phorus' trichloride, upon a carbazole c'ar boxylic' acid: and condensing the so obtained, CQIbitZOlOlC-fiClCl-Ellkylitlnlde Wlth a n1troso-. phenol in presence of sulfur c acld. r

3. The process'of preparing 2-carbazoloicacid-dimethyl-amido-indophenol which comprises reacting with dimethylamine in pres V ence of phosphorus-trichloride upon carbazole-Q-caibazoloic-acid and condensing the so obtained 2-carbazoloic acid-dimethyl-amide' With para-nitrosophenol' in, presence of sul- 4.1As new products the carbaZoloic-acid;

- alkylamido-indophenols, obtainable by reactingwith an aliphatic amine, havinga replaceable hydifoge n'atom linked tothe' nitrogen, upon a carbazole-carboxylic acid and condensing the carbazoloidacid filkylamide ALBERT SOHMELZER with a nitrosophenol,, wliich rcarbazolo'icacid-alkylamido-indophenols are reddish blue to bluepowders, soluble in concentrated sulfuric acid'with fromireddishblue to blue color and which in alkaline solution are readilyreduced with sodium sulfide or'hydro sul-;

fideto the correspondingleuco-compounds. "5; As a new product the 2-carbazoloic-acjiddimethylamido indophenol of thefollowing,

formula iso 

